References of "Raquez, Jean-Marie"
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See detailCO2-blown microcellular non-isocyanate polyurethane (NIPU) foams: from bio- and CO2-sourced monomers to potentially thermal insulating materials
Grignard, Bruno ULg; Thomassin, Jean-Michel ULg; Gennen, Sandro ULg et al

in Green Chemistry (2016), 18(7), 2206-2215

Bio- and CO2-sourced non-isocyanate polyurethane (NIPU) microcellular foams were prepared using supercritical carbon dioxide (scCO2) foaming technology. These low-density foams offer low thermal ... [more ▼]

Bio- and CO2-sourced non-isocyanate polyurethane (NIPU) microcellular foams were prepared using supercritical carbon dioxide (scCO2) foaming technology. These low-density foams offer low thermal conductivity and have an impressive potential for use in insulating materials. They constitute attractive alternatives to conventional polyurethane foams. We investigated CO2’s ability to synthesize the cyclic carbonates that are used in the preparation of NIPU by melt step-growth polymerization with a bio-sourced amino-telechelic oligoamide and for NIPU foaming. Our study shows that CO2 is not only sequestered in the material for long-term application, but is also valorized as a blowing agent in the production of NIPU foams. Such foams will contribute to energy conservation and savings by reducing CO2 emissions. [less ▲]

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See detailNon-isocyanate polyurethanes from carbonated soybean oil Using monomeric or oligomeric diamines To achieve thermosets or thermoplastics
Poussard, Loïc; Mariage, J.; Grignard, Bruno ULg et al

in Macromolecules (2016), 49(6), 2162-2171

Fully bio- and CO2-sourced non-isocyanate polyurethanes (NIPUs) were synthesized by reaction of carbonated soybean oil (CSBO) either with biobased short diamines or amino-telechelic oligoamides derived ... [more ▼]

Fully bio- and CO2-sourced non-isocyanate polyurethanes (NIPUs) were synthesized by reaction of carbonated soybean oil (CSBO) either with biobased short diamines or amino-telechelic oligoamides derived from fatty acids to achieve respectively thermoset or thermoplastic NIPUs. Biobased carbonated vegetable oils were first obtained by metal-free coupling reactions of CO2 with epoxidized soybean oils under supercritical conditions (120 °C, 100 bar) before complete characterization by FTIR, 1H NMR, and electrospray ionization mass spectroscopy (ESI-MS). In a second step, biobased NIPUs were produced by melt-blending of the so-produced cyclocarbonated oil with the biobased aminated derivatives. The thermal and mechanical properties of resulting polymers were found to be depending on the cyclocarbonated vegetable oil/amine ratio. More precisely, short diamines and CSBO led to the formation of cross-linked NIPUs, and the resulting tensile and thermal properties were poor. In contrast, elastomeric NIPUs derived from oligoamides and CSBO exhibited a better rigidity, an improved elongation at break (εr up to 400%), and a higher thermal stability (T95 wt% > 350 °C) than those of starting oligoamides. These results are impressive and highlight the potentiality of this environmental friendly approach to prepare renewable NIPU materials of high performances. [less ▲]

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See detailDesign of cross-linked semicrystalline poly(ε-caprolactone)-based networks with one-way and two-way shape-memory properties through Diels–Alder
Raquez, Jean-Marie; Vanderstappen, Sophie; Meyer, Franck et al

in Chemistry : A European Journal (2011), 17(36), 10135-10143

Cross-linked poly(ε-caprolactone) (PCL)-based polyesterurethane (PUR) systems have been synthesized through Diels–Alder reactions by reactive extrusion. The Diels–Alder and retro-Diels–Alder reactions ... [more ▼]

Cross-linked poly(ε-caprolactone) (PCL)-based polyesterurethane (PUR) systems have been synthesized through Diels–Alder reactions by reactive extrusion. The Diels–Alder and retro-Diels–Alder reactions proved to be useful for enhancing the molecular motion of PCL-based systems, and therefore their crystallization ability, in the design of cross-linked semicrystalline polymers with one-way and two-way shape-memory properties. Successive reactions between alpha,omega-diol PCL (PCL2), furfuryl alcohol, and methylene diphenyl 4,4′-diisocyanate straightforwardly afforded the alpha,omega-furfuryl PCL-based PUR systems, and subsequent Diels–Alder reactions with N,N-phenylenedimaleimide afforded the thermoreversible cycloadducts. The cross-linking density could be modulated by partially replacing PCL-diol with PCL-tetraol. Interestingly, the resulting PUR systems proved to be semicrystalline cross-linked polymers, the melting temperature of which (close to 45 °C) represented the switching temperature for their shape-memory properties. Qualitative and quantitative measurements demonstrated that these PUR systems exhibited one-way and two-way shape-memory properties depending on their cross-linking density. [less ▲]

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See detailThermoreversibly crosslinked poly(ε-caprolactone) as recyclable shape-memory polymer network
Defize, Thomas ULg; Riva, Raphaël ULg; Raquez, Jean-Marie et al

in Macromolecular Rapid Communications (2011), 32(16), 1264-1269

A new concept to build shape memory polymers (SMP) combining outstanding fixity and recovery ratios (both above 99% after only one training cycle) typical of chemically crosslinked SMPs with ... [more ▼]

A new concept to build shape memory polymers (SMP) combining outstanding fixity and recovery ratios (both above 99% after only one training cycle) typical of chemically crosslinked SMPs with reprocessability restricted to physically crosslinked SMPs is demonstrated by covalently bonding, through thermoreversible Diels–Alder (DA) adducts, star-shaped poly(epsilon-caprolactones) (PCL) end-functionalized by furan and maleimide moieties. A PCL network is easily prepared by melt-blending complementary end-functional star polymers in retro DA regime, then by curing at lower temperature to favour the DA cycloaddition. Such covalent network can be reprocessed when heated again at the retro DA temperature. The resulting SMP shows still excellent shape memory properties attesting for its good recyclability. [less ▲]

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See detailOxidative degradations of oxodegradable LDPE enhanced with thermoplastic pea starch: thermo-mechanical properties, morphology, and UV-ageing studies
Raquez, Jean-Marie; Bourgeois, Aurore; Jacobs, Heidi et al

in Journal of Applied Polymer Science (2011), 122(1), 489496

The abiotic UV-degradation behavior of oxodegradable LDPE was investigated in the presence of thermoplastic pea starch (TPPS) in this study. Oxodegradable LDPE was first melt-blended with thermoplastic ... [more ▼]

The abiotic UV-degradation behavior of oxodegradable LDPE was investigated in the presence of thermoplastic pea starch (TPPS) in this study. Oxodegradable LDPE was first melt-blended with thermoplastic pea starch (TPPS) using an internal mixing chamber to enhance the abiotic oxidative degradation of oxodegradable LDPE. Because of their different affinity, maleated polyethylene was added as compatibilizer. Tensile properties, thermal properties, and morphology of resulting melt-blends were determined at different content in TPPS. High content in TPPS (40 wt %) could be readily added to oxodegradable LDPE without affecting the tensile properties of resulting melt-blends. UV-ageing studies on compatibilized TPPS/oxodegradable LDPE melt-blends were carried out by Attenuated Total Reflectance infrared spectroscopy (ATR-FTIR), Dynamic Thermomechanical Analyses (DMTA) and Differential Scanning Calorimetry (DSC) under abiotic conditions. These results suggested a synergistic effect on the UV-ageing of TPPS-based melt-blends provided by both components during the first stage of UV-irradiation. [less ▲]

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See detailSupramolecular design of high-performance poly(L-lactide)/carbon nanotube nanocomposites: from melt-processing to rheological, morphological and electrical properties
Manfredi, Erica; Meyer, Franck; Verge, Pierre et al

in Journal of Materials Chemistry (2011), 21(40), 16190-16196

The ability of omega-imidazolium functionalized poly(L-lactide) (ImPLLA) chains to improve the CNT dispersion within the PLLA matrix was demonstrated in bulk and at elevated temperatures using melt ... [more ▼]

The ability of omega-imidazolium functionalized poly(L-lactide) (ImPLLA) chains to improve the CNT dispersion within the PLLA matrix was demonstrated in bulk and at elevated temperatures using melt-processing techniques. This approach brings new supramolecular tools to the formation of CNT-based biomaterials derived from renewable resources with outstanding properties for semi-industrial applications. In this work, the PLLA/CNT nanocomposites were prepared using extrusion technology, starting from masterbatches. The rheological, morphological, electrical properties as well as Raman analyses confirmed the establishment of supramolecular cation-pi interactions between ImPLLA and CNT in the melt, leading to a fine dispersion of CNT within PLLA matrix. [less ▲]

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See detailFrom polyester grafting onto POSS nanocage by ring-opening polymerization to high performance polyester/POSS nanocomposites
Goffin, Anne-Lise; Duquesne, Emmanuel; Raquez, Jean-Marie et al

in Journal of Materials Chemistry (2010), 20

Polyester-grafted polyhedral oligomeric silsesquioxane (POSS) nanohybrids selectively produced by ring-opening polymerization of epsilon-caprolactone and L,L-lactide (A.-L. Goffin, E. Duquesne, S. Moins ... [more ▼]

Polyester-grafted polyhedral oligomeric silsesquioxane (POSS) nanohybrids selectively produced by ring-opening polymerization of epsilon-caprolactone and L,L-lactide (A.-L. Goffin, E. Duquesne, S. Moins, M. Alexandre, Ph. Dubois, Eur. Polym. Journal, 2007, 43, 4103) were studied as ‘‘masterbatches’’ by melt-blending within their corresponding commercial polymeric matrices, i.e., poly(epsilon-caprolactone) (PCL) and poly(L,L-lactide) (PLA). For the sake of comparison, neat POSS nanoparticles were also dispersed in PCL and PLA. The objective was to prepare aliphatic polyester-based nanocomposites with enhanced crystallization behavior, and therefore, enhanced thermo-mechanical properties. Wide-angle X-ray scattering and transmission electron microscopy attested for the dispersion of individualized POSS nanoparticles in the resulting nanocomposite materials only when the polyester-grafted POSS nanohybrid was used as a masterbatch. The large impact of such finely dispersed (grafted) nanoparticles on the crystallization behavior for the corresponding polyester matrices was noticed, as evidenced by differential scanning calorimetry analysis. Indeed, well-dispersed POSS nanoparticles acted as efficient nucleating sites, significantly increasing the crystallinity degree of both PCL and PLA matrices. As a result, a positive impact on thermo-mechanical properties was highlighted by dynamic mechanical thermal analysis. [less ▲]

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